The present invention refers to a new process for fractionation of vegetable oils giving a confectionary fat as well as a product enriched in unsaponifiable components.
In the fractionation of vegetable oils to obtain a main fraction suitable for the manufacture of confectionary fats different liquid side fractions are also obtained. Said side fractions, the composition of which varies with the starting oil and the fractionation conditions, have been used in the food industry, for example for the preparation of emulsifiers, but are in general regarded as of little value.
It is well known that vegetable oils and fats contain a large number of biologically active components in addition to the dominating triglycerides. Such components are for instance polar lipids, that is phospholipids, sphingolipids and galactolipids, as well as more or less nonpolar lipid components such as phytosterols, triterpene alcohols and aliphatic alcohols, tocopherols, vitamin E for instance, and tocotrienols. The unsaponifiable part of the oil, by definition the material from a lipid sample which can be extracted by petroleum ether or diethyl ether after alkaline hydrolysis, is typically said to comprise said nonpolar to semi-polar lipids, hydrocarbons and waxes.
The unsaponifiable components of many vegetable oils are known to have different properties of interest for use in cosmetic and pharmaceutical preparations (Wachter, R., et al., Phytosterolexe2x80x94pflanzliche Wirkstoffe in der Kosmetik, Parfxc3xcmerie und Kosmetik, 75. Jahrgang, Nr. 11/94). The natural content and composition of the unsaponifiable lipid components in vegetable oils is unique for each raw material. The functionality of different concentrates enriched in unsaponifiable product is explained by the respective composition of said components, mainly tocopherols, phytosterols and triterpene esters.
Shea butter, for instance, has an unusually high content of unsaponifiable matter, up to 13%, hydrocarbons inclusive. The unsaponifiable lipids of shea butter are characterized by a high content of UV-absorbing triterpene esters and natural phytosterols claimed to impose anti-inflammatory effects on damaged skin.
The unsaponifiable lipids of rapeseed oil are dominated by a unique high content of sterols, such as xcex2-sitosterol, campesterol and brassicasterol, as well as tocopherols known to offer a good natural protection against oxidation. An unsaponifiable fraction of rapeseed oil has proven to show an anti-inflammatory effect on irritated skin (Lodxc3xa9n, M., et al., Effect of topically applied lipids on surfactant-irritated skin, British Journal of Dermatology 1996; 134: 215-220).
In the manufacturing of raw material for the food industry many of the unsaponifiable components in the vegetable fat or oil are negatively affected by the processing conditions and others are removed. The content of unsaponifiable components varies with the origin of the raw material. Typically the non glyceride part of a refined oil amounts to 0.5-1.0% by weight.
In order to obtain the unsaponifiable, biologically active components of interest there are different ways to proceed. The oil can for instance be saponified and components of interest extracted, which process will however produce large amounts of fatty acids and glycerol. In addition some of the components, for instance esters of sterols and triterpene alcohols will become saponified and lose their oil solubility. Another method is steam distillation of the oil and processing of the distillate. In this method the oil is under low pressure blown with steam which takes away volatile components, more or less, depending on the pressure and the temperature. However, also triglycerides and fatty acids are taken away and the. distillate has to be subjected to a saponification and extraction procedure, alternatively to a short path distillation, in order to purify the components of interest. By this the activity and quality of the components are reduced. Still another method is to fractionate the oil in a suitable solvent at a low temperature. This is a preferred process as the active components can be obtained or concentrated without being chemically modified.
Processes for fractionating oils and fats have since long been used for the manufacturing of confectionary fats or hard butters and also for obtaining fractions having certain specific characteristics. The liquid products which are obtained as by-products have been used in the food industry. In the processing of a vegetable oil one or more of the following steps are normally used:
pressing or extraction of the raw material;
refining of the pressed or extracted oil, that is degumming with acid to remove the polar lipids, deacidification with alkali to remove free fatty acids, and bleaching to reduce colour and oxidation products;
catalytic hydrogenation;
solvent fractionation of the hydrogenated oil bringing the triglycerides to precipitate;
deodorization by means of steam to remove components that give rise to unwanted flavours and odours.
U.S. Pat. No. 2,972,541, for instance, refers to hard butters and a method for preparing said hard butters by solvent fractionation from oils composed of essentially triglycerides of fatty acids of 16 and 18 carbon atoms. In order to recover triglycerides of interest the starting oil is hydrogenated to convert the fatty acid radicals of the oil from cis to trans figuration and to lower the initial unsaturation by eliminating most of the polyethenoic unsaturation. The hydrogenated oil can then be solvent fractionated, a technique well known in the glyceride oil art, to give a crystalline hard butter fraction. Nothing is, however, stated about the unsaponifiable fraction or the content of non-triglycerides in the oil.
EP-B1-0690904 refers to a process for the preparation of fractions of a fat of vegetable origin enriched with unsaponifiable materials, which process is characterized in that the fat is treated with a polar solvent such as acetone and heated giving a first fraction insoluble in hot solvent which is rich in unsaponifiable material. Said first fraction can be combined with a second fraction obtained from the soluble fraction after crystallization thereof at a temperature below 0xc2x0 C., preferably at xe2x88x9215 to xe2x88x9230xc2x0 C., filtration and evaporation of the filtrate. The obtained fraction enriched in unsaponifiable material is said to be useful for the preparation of cosmetical and pharmaceutical compositions, but nothing is stated about the utility of the solid fractions. The fat described is shea butter.
WO 96/03137 refers to cosmetic and pharmaceutical preparations containing shea butter concentrates having an increased content of components which can not be saponified. Said shea concentrates have been produced from raw or refined shea butter by distillation in a short path distiller at a temperature of 200-300xc2x0 C. and at a reduced pressure. It is also said to be possible to produce adequate concentrates by extraction of shea butter with organic solvents such as ethanol. In this process the original composition of the unsaponifiable components will, however, be destroyed as the esters are hydrolysed, oxidised and/or isomerised.
There is still a need of a process from which it will be possible to obtain, in addition to one or more hard fractions suitable for confectionary applications, a useful side fraction, such as a liquid fraction rich in chemically unaltered, unsaponifiable, biologically active components from vegetable oils in a cost effective way.
The present invention refers to a process for fractionation of a vegetable oil in order to obtain one or more steeply melting solid fractions suitable for confectionary applications as well as a liquid fraction rich in unsaponifiable, biologically active components.
In order to prepare confectionary fats, as well as a fraction rich in unsaponifiable, biologically active components, from a vegetable oil the oily raw material should be treated by the following steps in any suitable order: xe2x80x94pretreatment, that is pressing or extraction of the oil, refining, that is degumming with acid, deacidification and bleaching;
optional catalytic hydrogenation;
fractionation; and
after-treatment.
The invention refers to a process for fractionation of a vegetable oil giving one or more solid fractions suitable for confectionary applications a well as a liquid fraction rich in unsaponifiable, biologically active components, wherein an optionally pretreated oil having a melting point of 32-55xc2x0 C. is mixed with solvent in a ratio of 1:3-7 (w/v), heated to transparency, and then cooled at a rate of 0.1-1.5xc2x0 C./min and filtrated in one or more steps to a first fractionation temperature of xe2x88x925 to +10xc2x0 C., at which temperature one or more precipitated solid fractions suitable for use in confectionary applications have been filtered off giving a filtrate F1, characterised in that
a) the filtrate F1 optionally is mixed with additional solvent;
b) the filtrate F1 is cooled at a rate of 0.1-1.0xc2x0 C./min to a second fractionating temperature of xe2x88x9230 to xe2x88x9215xc2x0 C., at which temperature the precipitated solid -fraction is filtered off giving a filtrate F2;
c) the filtrate F2 is distilled to remove the solvent giving a liquid fraction in which the unsaponifiable, biologically active components have been enriched by at least a factor 2.
It has surprisingly been found that a repeated fractionation at a low temperature as described above will bring about an enrichment of the unsaponifiable components of a vegetable oil in the final liquid phase to an extent far superior to what could be expected. This must be ascribed to the fact that the desired, unsaponifiable components in spite of high melting points surprisingly are soluble in the liquid triglycerides present in the vegetable oils also at very low temperatures and therefore can be enriched to a higher than expected level of concentration.
Cocoa butter alternatives, CBA, are usually divided into 3 categories, that is Cocoa Butter Equivalents, CBE, Cocoa Butter Replacers, CBR, and Cocoa Butter Substitutes, CBS, depending on their compatibility and structural similarity to cocoa butter. Cocoa butter equivalents are characterised by a triglyceride composition dominated by the same combinations of stearic, oleic and palmitic acid based triglycerides that are found in cocoa butter (SOS, POS, and POP, where S stands for stearic, O for oleic and P for palmitic and the three letter combination defines a triglyceride). The crystallisation behaviour of these fats is also identical to that of cocoa butter. CBE""s are manufactured from fats like shea butter, illipe butter, mango kernel oil, sal butter, madhuca butter and other similar fats, alone or in combination with fractionated palm oils.
Cocoa butter replacers, CBR, are used in combination with 5-35% cocoa butter in confectionary products. The chemical composition of CBRs is dominated by combinations of oleic, elaidic, stearic and palmitic acids in the triglycerides (PEP, PEO, and SEE, where E stands for elaidic acid) with a lower degree of compatibility with the cocoa butter tri-glycerides. CBRs do not need the characteristic tempering procedure necessary to obtain the correct crystal form in cocoa butter. CBRs are obtained by hydrogenating and optionally fractionating poly- and monounsaturated oils like soybean oil, cottonseed oil, rapeseed oil and groundnut oil.
Cocoa butter substitutes, CBS, have a triglyceride structure derived from shorter fatty acids (lauric and myristic) and are thus completely incompatible with cocoa butter. They are mainly derived from palm kernel oil and coconut oil by combinations of fractionation and hydrogenation.
The solid fractions obtained by the process of the invention can be used to formulate cocoa butter equivalents and cocoa butter replacers according to the description above. For example the solid fraction obtained from shea nut oil at the second fractionation temperature can be used to formulate a CBE composition, especially if combined with the solid fraction obtained at the first fractionation temperature. These high melting fractions are also characterised by a low content of unsaponifiable matter, especially triterpene alcohol esters, which improves the tempering properties and the compatibility with cocoa butter. If a hydrogenated rapeseed oil is used as starting material for the fractionation a CBR type of product can be obtained by combination of the solid fractions filtrated at the first and the second fractionation temperatures.
Vegetable oils useful as raw materials are those oils which contain the active components in an amount that can be concentrated. Examples of raw materials containing lipids that can be enriched by the process of the invention are the following: rapeseed oil (Brassica napus, rapa, campestris etc), crambe oil (Crambe abyssinica, hispanica), mustard seed oil (Brassica alba, hirta, nigra, juncea, carinata), soybean oil (Glycine max), sunflower oil (Helianthus annuus), cottonseed oil (Gossypium hirsutum, barbadense, herbaceum), peanut (or groundnut, or arachis) oil (Arachis hypogaea), linseed oil (Linus usitatissimum), evening primrose oil (Oenothera biennis, larmarkiana), borage oil (Borago officinalis), grapeseed oil (Vitis vinifera), safflower oil (Carthamus tinctorius), sesame oil (Sesamum indicum, orientale), tea seed oil (Thea sasanqua, Camellia sasanqua), corn (or maize) oil, corn fibre oil, corn bran oil (Zea mays), wheat oil, wheat bran oil or wheat germ oil (Triticum aestivum), oat oil, oat bran oil (Avena sativa), rice bran oil, rice oil (oryza sativa), olive oil (Olea europea), palm oil, palm kernel oil (Elaeis guineensis, oleifera), coconut oil (Cocos nucifera), babassu oil (orbignya martiana, oleifera), illipe butter, Borneo tallow (Shorea stenoptera), shea butter or shea oil (Butyrospermum parkii), madhuca, mowrah butter (Madhuca latifolia, indica, longifolia), sal butter (Shorea robusta), mango seed oil (Mangifera indica), avocado oil, avocado seed oil (Persea americana), cocoa butter (Theobroma cacao), hazelnut oil (Corylus avellana), almond oil (Prunus amygdala), macadamia nut oil (Macadamia tetraphylla), walnut oil (Juglans nigra), and chestnut oil (Castanea mollissima).
Preferred examples of such oils are shea butter or shea oil, rapeseed oil, canola oil, olive oil, avocado oil, peanut oil, corn oil, soybean oil, sunflower oil, hybrid sunflower oil, wheat-germ oil, illipe butter, mango kernel oil, shorea butter, sal butter, sesame oil, rice bran oil, safflower oil, linseed oil, palm oil, palm kernel oil, coconut oil, cocoa butter, cottonseed oil, oat oil, oat bran oil, as well as mixtures thereof. The oils having a naturally high content of the active components are preferred.
Unsaponifiable, biologically active components which can be enriched by the process of the invention include the following compounds of interest: retinol and acyl retinols; luteol and luteol esters; xcex2-carotene and other carotenoids; tocopherols and tocotrienols; phytosterols, such as 4,4-dimethyl sterols (triterpene alcohols), 4-monomethylsterols, 4-de(s)methylsterols and their esters with fatty acids, cinnamic acid, substituted cinnamic acids, benzoic acid, substituted benzoic acids; avenanthramide; oil soluble flavonoids; oil soluble vitamins and vitamin precursors (Vitamin D and A); ubiquinone, phylloquinones, menaquinones and oil soluble derivatives thereof. Sterols of interest are for example xcex2-sitosterol, stigmasterol, avenasterol, campesterol, brassicasterol, dihydrobrassicasterol, their ring saturated counter-parts (stanols) and esters with long chain saturated or unsaturated fatty acids. short chain carboxylic acids and aromatic acids. Triterpene alcohols include for example xcex2- and xcex2-amyrin, lupeol, parkeol, germanicol, taraxasterol, taraxerol, "psgr"-taraxasterol, butyrospermol, lanosterol, cycloartenol, cyclobranol, their ring saturated counterparts and esters with long chain unsaturated and saturated fatty acids, short chain carboxylic acids and aromatic acids, that is cinnamic, ferulic, caffeic, sinapic, benzoic and similar acids.
Depending on the lipid of interest and the intended functionality of the concentrate different raw materials and raw material combinations can be used. The following examples are given to illustrate the possibilities: Tocopherols are found, for example, in most polyunsaturated oils like rapeseed oil, soybean oil, corn oil, groundnut oil and sunflower oil. Tocotrienols are, for example, found in oils derived from the oil palm (Elaeis sp). Triterpene alcohols (4,4-dimethyl sterols) are found in, for example, shea butter, olive oil, rice bran oil. 4-monomethylsterols and 4-demethylsterols are common in all vegetable oils and fats, either as free sterols or esterified to fatty acids or phenolic acids.
The oil obtained from the pressing or extraction is refined carefully to preserve the active components intact. This is best done by conventional chemical refining, that is alkalic refining. The crude oil is degummed by means of phosphoric acid or citric acid, is deacidified with an aqueous solution of sodium, potassium or calcium hydroxide, and finally bleached with bentonite or silicagel. Said processes take place at a temperature of 50-90xc2x0 C.
When fats or oils having a high content of unsaturated components are used as raw material it is preferable in order to obtain the characteristic, effective separation of the active components to reduce the solubility of the triglycerides by catalytic hydrogenation. Hydrogenation of vegetable oils suitable for fractionation is done using commercial Ni-containing catalysts such as Pricat 9900, Pricat 9910, Pricat 9908 and Pricat 9918 from Unichema, Nysosel 325, Nysosel 545, Nysosel 645, Nysosel 222, Nysel SP 7 and Nysel SP10 from Engelhard or G111, G95-D and KE/KTR from Sud-Chemie. It is also possible to use Pd or Pt on a carbon carrier (Pd/C or Pt/C). The hydrogenation is normally carried out using 0.005-0.15% Ni in oil at 180-220xc2x0 C. and a partial pressure of hydrogen of 1.0-4.0 bar.
The hydrogenation is allowed to proceed to a melting point of 32-55xc2x0 C., which implies that most of the unsaturated triglycerides have become sufficiently saturated to be solid, which makes it possible to have them removed in the solid phase in the subsequent fractionation step.
According to another aspect the invention refers to a process for fractionation of a vegetable oil or a fraction thereof comprising the additional step of catalytically hydrogenating the oil or a liquid fraction thereof in order to increase the melting point to a value within the range of 32-55xc2x0 C.
If the melting point of the oil is more than 55xc2x0 C., the amount of liquid to solubilise the desired components will be too small and they will be precipitating together with the solid triglycerides. The recovery of the small amount of the liquid fraction will also be more difficult than if a lower melting point is used. However, if the melting point of the starting material is too low, that is below 32xc2x0 C., the concentration of the desired lipids in the liquid fraction will be too low and the desired enrichments cannot be achieved.
When the raw material oil or fat contains a large amount of saturated fats, such as shea butter, cacao butter or illipe butter, this hydrogenation step is optional, but a higher melting point of the oil will give a higher enrichment of the product.
If the vegetable oil used as a starting oil has a melting point of 38-55xc2x0 C. the second fractionation temperature can be as high as xe2x88x925xc2x0 C., but if, on the other hand, the melting point of the oil is as low as 32-40xc2x0 C. the second fractionation temperature must be lower, that is from xe2x88x9230 to xe2x88x9215xc2x0 C.
The fractionation is performed by mixing the oil with a semipolar solvent, such as a ketone, for example acetone or methylethyl ketone, methylisobutyl ketone, diethyl ketone, 2-nitropropane, tetrahydrofuran or ethyl acetate, a nonpolar solvent, such as hexane or petroleum ether, or a polar solvent, such as an alcohol, such as isopropanol, ethanol or methanol, into a slurry which is cooled in a controlled way to a first fractionation temperature, generally above 0xc2x0 C., preferably at about xe2x88x925xc2x0 C. to +10xc2x0 C., at which temperature part of the fat, especially the hydrogenated or saturated triglycerides are being precipitated as one or more solid fractions. Said fractions are filtrated and the filtrate containing a liquid fraction enriched in biologically active components saved.
In a second step this filtrate is fractionated once more at a second, still lower fractionation temperature, about xe2x88x9215 to xe2x88x9230xc2x0 C., at which temperature another solid phase is precipitated giving a filtrate containing a liquid fraction of a still higher concentration of active components. Subsequently the solvent is removed from the filtrate by distillation. In order to increase the concentration of unsaponifiable components the liquid fraction can be hydrogenated once more before a second fractionation.
The after-treatment comprises a deodorization of the oil by heating under low pressure, for instance at 150-230xc2x0 C. and 100-500 Pa, adding steam. The low temperature is necessary to maintain the active components in the oil. By this treatment unpleasant odours and flavourings are removed, as well as optional residues of solvents or pesticides etc.
According to another aspect the invention also refers to a process for fractionation of a vegetable oil giving one or more solid fractions suitable for confectionary applications a well as a liquid fraction rich in unsaponifiable, biologically active components, wherein an optionally pretreated oil having a melting point of 32-55xc2x0 C. is mixed with solvent in a ratio of 1:3-7 (w/v), heated to transparency, and then cooled at a rate of 0.1-1.5xc2x0 C./min and filtrated in one or more steps to a first fractionation temperature of xe2x88x925 to +10xc2x0 C., at which temperature one or more precipitated solid fractions suitable for use in confectionary applications have been filtered off giving a filtrate F1, which is characterised in that
a) the filtrate F1 is evaporated and the liquid fraction hydrogenated to a melting point of 32-55xc2x0 C.;
b) the hydrogenated liquid fraction is mixed with solvent in a ratio of 1:3-7 (w/v), heated to transparency and then cooled at a rate of 0.5-1.0xc2x0 C./min and filtrated in one or more steps to a fractionation temperature of xe2x88x925 to +10xc2x0 C., at which temperature a solid fraction is filtered off giving a filtrate HF1;
c) the filtrate HF1 is cooled at a rate of 0.1-1.0xc2x0 C./min, optionally after mixing with additional solvent to a second fractionation temperature of xe2x88x9230 to xe2x88x9215xc2x0 C., at which temperature a solid fraction is filtered off giving a filtrate F2;
d) the filtrate F2 is distilled to remove the solvent giving a liquid fraction in which the unsaponifiable, biologically active components have been enriched by at least a factor 4.
According to a preferred process shea butter is fractionated giving one or more solid fractions suitable for confectionary applications as well as a liquid fraction rich in unsaponifiable biologically active components, wherein optionally pretreated shea butter having a melting point of 32-38xc2x0 C. is mixed with acetone in a ratio of 1:4-6 (w/v), heated to transparency, and then cooled at a rate of 0.1-0.5xc2x0 C./min and filtrated in one or more steps to a first fractionation temperature of +1 to +8xc2x0 C., at which temperature one or more solid fractions suitable for use in confectionary applications have been filtered off giving a filtrate F1, which process is characterized in that
a) the filtrate F1 optionally is mixed with additional acetone;
b) the filtrate F1 is cooled at a rate of 0.1-1.0xc2x0 C./min to a second fractionation temperature of xe2x88x9225 to xe2x88x9215xc2x0 C. at which temperature the precipitated solid fraction is filtered off giving a filtrate F2;
c) the filtrate F2 is distilled to remove the solvent giving a liquid fraction in which the unsaponifiable, biologically active components have been enriched by at least a factor 3.
According to another preferred process rapeseed oil is fractionated giving one or more solid fractions suitable for confectionary applications as well as a liquid fraction rich in unsaponifiable biologically active components, wherein an optionally pretreated rapeseed oil hydrogenated to a melting point of 38-48xc2x0 C. is mixed with acetone in a ratio of 1:4-6 (w/v), heated to transparency, and then cooled at a rate of 0.1-0.5xc2x0 C./min and filtrated in one or more steps to a first fractionation temperature of xe2x88x925 to +10xc2x0 C., at which temperature one or more solid fractions suitable for use in confectionary applications have been filtered off giving a filtrate F1, which process is characterized in that
a) the filtrate F1 optionally is mixed with additional acetone;
b) the filtrate F1 is cooled at a rate of 0.1-1.0xc2x0 C./min to a second fractionation temperature of xe2x88x9225 to xe2x88x9215xc2x0 C. at which temperature the precipitated solid fraction is filtered off giving a filtrate F2;
c) the filtrate F2 is distilled to remove the solvent giving a liquid fraction in which the unsaponifiable, biologically active components have been enriched by at least a factor 3.
The invention also refers to a liquid vegetable oil fraction rich in biologically active components which can be obtained by the fractionation process of the invention. The liquid vegetable oil fraction has been enriched by a factor of at least 2.0 in biologically active components comprising:
tocopherols and tocotrienols and dimers and isomers thereof;
sterols, methyl sterols, dimethyl sterols, triterpene alcohols and esters thereof with saturated, monounsaturated or polyunsaturated fatty acids having a hydrocarbon chain length of 6-24 carbon atoms and 0 to 6 double bonds, and esters thereof with cinnamic acid or hydroxy and/or methoxy substituted cinnamic acids;
carotenoids and isomers thereof.
A preferred aspect of the invention is a shea butter fraction which can be obtained by the process of the invention, which comprises 64-85% by weight di- and triglycerides and 15-33% by weight unsaponifiable lipid components. In said-shea butter fraction the biologically active components comprise
cinnamic esters of triterpene alcohols, 10-25%
fatty acid esters of triterpene alcohols, 5-10%
squalene and other hydrocarbons, less than 1.0% based on the total weight of the concentrate.
Another preferred aspect of the invention is a liquid rapeseed oil fraction rich in biologically active components which can be obtained by the process of the invention and which contains 1.5 to 5% unsaponifiable components, the rest being tri- and diglycerides.
In the rapeseed oil fraction of the invention the unsaponifiable components comprise
at least 2000 ppm of mixed tocopherol isomers in their naturally occurring proportions and
not less than 1.3% sterols and sterol esters, the sterol composition being dominated by xcex2-sitosterol, campesterol and brassicasterol in their naturally occurring proportions.
The shea butter fraction of the invention can be used as an ingredient of a cosmetical or pharmaceutical preparation, especially for providing UV-protecting and skin moisturizing properties. The enriched content of UV-B absorbing cinnamic acid esters offers an additive effect when combined with commercial sun screens such as octyl methoxycinnamate. An improved photo protection from the combination of the natural substance with a chemical sun screen or a physical filter in a skin care formulation can be obtained. The triterpene alcohols and phytosterols, which have been enriched in the fraction, have an anti-inflammatory action. These substances also have a stabilising effect on cell membranes, which improves the water binding capacity of the epidermis, giving a desired moisturising effect. The triglyceride oil present in the fraction provides emollience and lubricity.
The rapeseed oil fraction of the invention can also be used as an ingredient of a cosmetical or pharmaceutical preparation, The high content of enriched natural tocopherols results in an excellent oxidation stability to the oil fraction, Oil Stability Index (OSI) greater than 100 hours at 110xc2x0 C. The tocopherols, as free radical scavengers, also offers a protection of other ingredients in a formulation as well as a biochemical protection of epidermal cells from photo-damage. Particularly UV-A protecting properties have been demonstrated by the rapeseed oil fraction. Tocopherols in combination with phytosterols are further known to show membrane stabilising properties resulting in improved water binding capacity of the epidermis. Shown anti-inflammatory properties on surfactant damage skin is also related to the epidermis. An anti-irritant and anti-inflammatory effect on damaged skin can also be attributed to the combination of phytosterols and tocopherols.